Cyclohexenone derivatives, preparation and use thereof as herbicides

ABSTRACT

Cyclohexenone derivative of the formula ##STR1## where A is oxygen or NOR 8 , where R 8  is alkyl, alkenyl, alkynyl, haloalkyl or haloalkenyl, chlorothienyl or alkoxyalkyl 
     B is O, S, SO or SO 2 , 
     X is hydrogen or methoxycarbonyl, 
     R 1  is hydrogen, carbonylalkyl, benzoyl or a cation, 
     R 2  is alkyl, 
     R 3  and R 4  are hydroxyl, chlorine, bromine, thioalkylcarboxyl, thiocarbonylalkyl, alkylcarbonyloxy, alkoxy, or alkylthio, or R 3  and R 4  together epoxy, 
     R 5  and R 6  are hydrogen or methyl or R 5  and R 6  are together methyleneoxyethylene, and 
     R 7  is hydrogen or methyl, 
     and herbicides containing these compounds.

This application is a continuation of Ser. No. 07/277,208, filed Nov. 29, 1988, now abandoned, which is a divisional of Ser. No. 06/946,060, filed Dec. 24, 1986, now abandoned.

The present invention relates to novel cyclohexanone derivatives having a herbicidal action, to agents based on such cyclohexanone derivatives, and to processes for their preparation and use as herbicides.

The herbicidal action of oxime ethers having a cyclohexenone structure and nonaromatic substituents in the 5-position is known from EP 71,707.

It is further known that certain 2-acyl-3-hydroxycyclohex-2-en-1-ones regulate plant growth (EP 123,001 and EP 126,713).

We have found that cyclohexenone derivatives of the formula ##STR2## where A is oxygen or NOR⁸, where R⁸ is alkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, alkynyl of 3 or 4 carbon atoms, haloalkyl or haloalkenyl of 2 to 4 carbon atoms and 1 to 3 halogen atoms, chlorothienyl or alkoxyalkyl of 2 to 4 carbon atoms,

B is O, S, SO or SO₂,

X is hydrogen or methoxycarbonyl,

R¹ is hydrogen, carbonylalkyl of 2 to 18 carbon atoms or benzoyl or an inorganic or organic cation,

R² is alkyl of up to 4 carbon atoms,

R³ and R⁴, independently of each other, are each hydroxyl, chlorine, bromine, thioalkylcarboxyl, thiocarbonylalkyl, alkylcarbonyloxy each of up to 4 carbon atoms or R³ and R⁴ are together alkoxy of up to 3 carbon atoms and hydroxyl or together alkylthio of up to 3 carbon atoms and hydroxyl or together epoxy,

R⁵ and R⁶, independently of each other, are each hydrogen or methyl or R⁵ and R⁶ are together methyleneoxyethylene,

R⁷ is hydrogen or methyl,

have a powerful herbicidal action, preferably on species of the family of the grasses (Gramineae). They are compatible and thus selective in broad-leaf crops and also in monocotyledons which do not belong to the Gramineae. In addition, numerous compounds are also selective in Gramineae crops such as wheat and rice and at the same time control undesirable grasses. They are biologically superior to comparable compounds.

Examples of R¹ in the formula I are: hydrogen, acetyl, propionyl, butyryl, pivaloyl, palmitoyl, stearoyl, benzoyl, sodium, potassium, ammonium, calcium, magnesium, trialkylammonium, tetraalkylammonium, trialkylbenzylammonium, trialkylsulfonium and trialkylsulfoxonium.

Examples of R² in the formula I are: methyl, ethyl, n-propyl, i-propyl, n-butyl and i-butyl.

Examples of R³ and R⁴ are: alkoxy such as methoxy, ethoxy, n-propoxy or i-propoxy, alkylthio such as methylthio, ethylthio or n-propylthio, hydroxyl, bromine, chlorine, thioalkylcarboxyl such as thiomethylcarboxyl or thioethylcarboxyl, thiocarbonylalkyl such as thiocarbonylmethyl or thiocarbonylethyl, dimethylamino, acetoxy, propionyloxy, butyryloxy and epoxy.

Examples of R⁸ are: methyl, ethyl, n-propyl, i-propyl, allyl, (E)-2-butenyl, 2-fluoroeth-1-yl, 2-chloroeth-1-yl, (E)-3-chloro-2-propenyl, 1,1,2-trichloroprop-1-en-3-yl, chlorothienyl, propargyl, methoxymethyl and methoxyethyl.

The cyclohexenone derivatives of the formula I where A is NOR⁸ and R¹ is hydrogen can be obtained by reacting compounds of the formula ##STR3## where R², R³, R⁴, R⁵, R⁶, R⁷ and X have the abovementioned meanings, with alkoxyammonium compounds of the formula R⁸ ONH₃ Y, where Y is an anion. To this end the two reactants are reacted with each other, for example in a solvent in the presence of a base at from 0° C. to the boiling point of the solvent. Suitable bases are for example carbonates, hydrogencarbonates, acetates, alcoholates, oxides or hydroxides of alkali and alkaline earth metals, in particular sodium, potassium, magnesium or calcium, or organic bases, such as pyridine or tertiary amines.

Suitable solvents are for example dimethyl sulfoxide, alcohols such as methanol, ethanol or isopropanol, benzene, toluene, hydrocarbons and chlorohydrocarbons, such as chloroform, dichloroethane, hexane or cyclohexane, esters, such as ethyl acetate, or ethers, such as dioxane or tetrahydrofuran.

The reaction is complete within a few hours, and the reaction product can be isolated by concentrating the mixture, partitioning the residue between methylene chloride and water and distilling off the solvent under reduced pressure.

The compounds of the formula I where A is NOR⁸ and R¹ is hydrogen can also be obtained by reacting the compounds of the formula I where A is oxygen and R¹ is hydrogen with appropriate alkoxyamines of the formula R⁸ -ONH₂ in a suitable diluent; suitable reaction temperatures range in general from 15° to 70° C. The alkoxyamine can be used in the form of an aqueous solution; depending on the solvent used for the other reactant, a one- or two-phase reaction mixture is obtained.

Suitable solvents for the reaction are for example alcohols, such as methanol, ethanol, isopropanol or cyclohexanol, hydrocarbons and chlorohydrocarbons, such as hexane, cyclohexane, methylene chloride, toluene or dichloroethane, esters, such as ethyl acetate, nitriles, such as acetonitrile, and cyclic ethers, such as tetrahydrofuran.

Alkali metal salts of compounds I can be obtained by treating the compounds with alkaline compounds such as sodium hydroxide, potassium hydroxide, sodium alcoholate or potassium alcoholate in aqueous solution or in an organic solvent, such as methanol, ethanol, acetone or toluene.

Other metal salts, for example the managanese, copper, zinc, iron, calcium, magnesium and barium salts, can be prepared from the sodium salts in a conventional manner (by reaction with salts of the metals with inorganic acids), as in the same way the ammonium and phosphonium salts can be prepared by means of ammonia or phosphonium, sulfonium or sulfoxonium hydroxides.

The compounds of the formula I where A is oxygen can be prepared, for example from the corresponding cyclohexane-1,3-diones II ##STR4## by literature methods (Tetrahedron Lett. 29, (1975), 2491).

It is also possible to prepare compounds of the formula I where A is oxygen via the enol ester intermediate obtained on reacting compounds of the formula II with acid chlorides in the presence of bases and subsequently rearranged with certain imidazole or pyridine derivatives (Japanese Preliminary Published Application 79/063,052).

The compounds of the formula II can be obtained by literature method as given for example in German Laid-Open Application DOS 3,219,490.

It is also possible to introduce the substituents R³ and R⁴ at a later stage, preferably directly into compounds of the formula I where A is oxygen.

Suitable precursors are compounds of the formula ##STR5## where literature reactions can be carried out on the double bond, for example addition of halogens, hydrogen halides, mercaptans, thiolcarboxylic acids, mercaptocarboxylic acids or epoxidation.

The epoxy derivatives thus obtained can serve as starting materials for further syntheses based on opening the oxirane ring, for example reaction with mercaptans, water or alcohols with or without acid or base catalysis.

The compounds of the formula I where B is SO or SO₂ can also be obtained by oxidizing appropriate precursors where the sulfur is in a lower state of oxidation. Oxidizing agents are for example oxygen, ozone, peroxy compounds, such as hydrogen peroxides, per-acids, hydroperoxides, halogens, inorganic halogen compounds, such as hypochlorite, chlorate, nitrogen compounds, such as nitric acid and dinitrogen pentoxide, or salts of metals of higher valence, such as lead, bismuth, vanadium, manganese, chromium or cobalt salts. Anodic oxidation is also possible. The oxidation can be carried out not only at the final stage but, in principle, at any stage of the synthesis route described above.

The examples which follow illustrate the preparation of the novel compounds. Parts by weight relate to parts by volume as the kilogram relates to the liter.

EXAMPLE 1

14.8 parts by weight of 2-propionyl-5-(5,6-dihydro-2H-pyran-3-yl)-3-hydroxy-2-cyclohexen-1-one are dissolved in 100 parts by volume of dichloromethane, and m-chloroperbenzoic acid is added at room temperature, and the reaction is monitored by means of thin layer chromatography. After the reaction has ended, the precipitated m-chlorobenzoic acid is filtered off, the filtrate is washed twice with semiconcentrated sodium bicarbonate solution and water and dried over sodium sulfate, and the solvent is distilled off under reduced pressure to leave 2-propionyl-5-(3,4-epoxy-tetrahydropyran-3-yl)-3-hydroxy-2-cyclohexen-1-one (compound No. 30).

EXAMPLE 2

3.0 parts by weight of 2-propionyl-5-(3,4-epoxytetrahydropyran-3-yl)-3-hydroxy-2-cyclohex-1-one, 1.8 parts by weight of (E)-3-chloro-2-propenyloxyammonium chloride, 1.1 parts by weight of sodium bicarbonate and 100 parts by volume of methanol are stirred at room temperature for 16 hours. The solvent is distilled off under reduced pressure, 50 parts by volume of water and 50 parts by volume of dichloromethane are added to the residue, after vigorous stirring the phases are separated, and the organic phase is dried over sodium sulfate. Distilling off the solvent under reduced pressure leaves 2-[1-((E)-3-chloro-2-propenyloxyimino)propyl]-5-(3,4-epoxytetrahydropyran-3-yl)-3-hydroxy-2-cyclohexen-1-one (compound No. 401).

The following compounds can be obtained in a similar manner:

(The ¹ H-NMR data are given in δ (ppm) and relate to tetramethylsilane as internal standard. Abbreviations: s=singlet, d=dublet, m=multiplet, q=quartet).

                  TABLE 1                                                          ______________________________________                                          ##STR6##                                                                      No.  R.sup.1                                                                               R.sup.2  R.sup.3 and R.sup.4                                                                    B    .sup.1 H-NMR data                            ______________________________________                                          1   H      Methyl   Cl      S                                                  2   H      Methyl   Cl      O                                                  3   H      Methyl   Cl      SO                                                 4   H      Methyl   Cl      SO.sub.2                                           5   H      Methyl   Br      S                                                  6   H      Methyl   Br      O                                                  7   H      Methyl   Br      SO                                                 8   H      Methyl   Br      SO.sub.2                                           9   H      Methyl   OH      S                                                  10  H      Methyl   OH      O                                                  11  H      Methyl   OH      SO                                                 12  H      Methyl   OH      SO.sub.2                                           13  H      Methyl   Epoxy   S                                                  14  H      Methyl   Epoxy   O                                                  15  H      Methyl   Epoxy   SO                                                 16  H      Methyl   Epoxy   SO.sub.2                                           17  H      Ethyl    Cl      S                                                  18  H      Ethyl    Cl      O                                                  19  H      Ethyl    Cl      SO                                                 20  H      Ethyl    Cl      SO.sub.2                                           21  H      Ethyl    Br      S                                                  22  H      Ethyl    Br      O                                                  23  H      Ethyl    Br      SO                                                 24  H      Ethyl    Br      SO.sub.2                                           25  H      Ethyl    OH      S                                                  26  H      Ethyl    OH      O                                                  27  H      Ethyl    OH      SO                                                 28  H      Ethyl    OH      SO.sub.2                                           29  H      Ethyl    Epoxy   S                                                  30  H      Ethyl    Epoxy   O                                                  31  H      Ethyl    Epoxy   SO                                                 32  H      Ethyl    Epoxy   SO.sub.2                                           33  H      n-Propyl Cl      S                                                  34  H      n-Propyl Cl      O    1.0(t), 3.9(m), 4.4(m)                        35  H      n-Propyl Cl      SO                                                 36  H      n-Propyl Cl      SO.sub.2                                           37  H      n-Propyl Br      S                                                  38  H      n-Propyl Br      O    2.0(d), 3.0(m), 4.6(s)                        39  H      n-Propyl Br      SO                                                 40  H      n-Propyl Br      SO.sub.2                                           41  H      n-Propyl OH      S                                                  42  H      n-Propyl OH      O    1.0(t), 1.6(q), 3.8(m)                        43  H      n-Propyl OH      SO                                                 44  H      n-Propyl OH      SO.sub.2                                           45  H      n-Propyl Epoxy   S                                                  46  H      n-Propyl Epoxy   O                                                  47  H      n-Propyl Epoxy   SO                                                 48  H      n-Propyl Epoxy   SO.sub.2                                           49  H      n-Butyl  Cl      S                                                  50  H      n-Butyl  Cl      O                                                  51  H      n-Butyl  Cl      SO                                                 52  H      n-Butyl  Cl      SO.sub.2                                           53  H      n-Butyl  Br      S                                                  54  H      n-Butyl  Br      O                                                  55  H      n-Butyl  Br      SO                                                 56  H      n-Butyl  Br      SO.sub.2                                           57  H      n-Butyl  OH      S                                                  58  H      n-Butyl  OH      O                                                  59  H      n-Butyl  OH      SO                                                 60  H      n-Butyl  OH      SO.sub.2                                           61  H      n-Butyl  Epoxy   S                                                  62  H      n-Butyl  Epoxy   O                                                  63  H      n-Butyl  Epoxy   SO                                                 64  H      n-Butyl  Epoxy   SO.sub.2                                           65  Na.sup.+                                                                              Methyl   Cl      S                                                  66  Na.sup.+                                                                              Methyl   Cl      O                                                  67  Na.sup.+                                                                              Methyl   Cl      SO                                                 68  Na.sup.+                                                                              Methyl   Cl      SO.sub.2                                           69  Na.sup.+                                                                              Methyl   Br      S                                                  70  Na.sup.+                                                                              Methyl   Br      O                                                  71  Na.sup.+                                                                              Methyl   Br      SO                                                 72  Na.sup.+                                                                              Methyl   Br      SO.sub.2                                           73  Na.sup.+                                                                              Methyl   OH      S                                                  74  Na.sup.+                                                                              Methyl   OH      O                                                  75  Na.sup.+                                                                              Methyl   OH      SO                                                 76  Na.sup.+                                                                              Methyl   OH      SO.sub.2                                           77  Na.sup.+                                                                              Methyl   Epoxy   S                                                  78  Na.sup.+                                                                              Methyl   Epoxy   O                                                  79  Na.sup. +                                                                             Methyl   Epoxy   SO                                                 80  Na.sup.+                                                                              Methyl   Epoxy   SO.sub.2                                           81  Na.sup.+                                                                              Ethyl    Cl      S                                                  82  Na.sup.+                                                                              Ethyl    Cl      O                                                  83  Na.sup.+                                                                              Ethyl    Cl      SO                                                 84  Na.sup.+                                                                              Ethyl    Cl      SO.sub.2                                           85  Na.sup.+                                                                              Ethyl    Br      S                                                  86  Na.sup.+                                                                              Ethyl    Br      O                                                  87  Na.sup.+                                                                              Ethyl    Br      SO                                                 88  Na.sup.+                                                                              Ethyl    Br      SO.sub.2                                           89  Na.sup.+                                                                              Ethyl    OH      S                                                  90  Na.sup.+                                                                              Ethyl    OH      O                                                  91  Na.sup.+                                                                              Ethyl    OH      SO                                                 92  Na.sup.+                                                                              Ethyl    OH      SO.sub.2                                           93  Na.sup.+                                                                              Ethyl    Epoxy   S                                                  94  Na.sup.+                                                                              Ethyl    Epoxy   O                                                  95  Na.sup.+                                                                              Ethyl    Epoxy   SO                                                 96  Na.sup.+                                                                              Ethyl    Epoxy   SO.sub.2                                           97  Na.sup.+                                                                              n-Propyl Cl      S                                                  98  Na.sup.+                                                                              n-Propyl Cl      O                                                  99  Na.sup.+                                                                              n-Propyl Cl      SO                                                100  Na.sup.+                                                                              n-Propyl Cl      SO.sub.2                                          101  Na.sup.+                                                                              n-Propyl Br      S                                                 102  Na.sup.+                                                                              n-Propyl Br      O                                                 103  Na.sup.+                                                                              n-Propyl Br      SO                                                104  Na.sup.+                                                                              n-Propyl Br      SO.sub.2                                          105  Na.sup.+                                                                              n-Propyl OH      S                                                 106  Na.sup.+                                                                              n-Propyl OH      O                                                 107  Na.sup.+                                                                              n-Propyl OH      SO                                                108  Na.sup.+                                                                              n-Propyl OH      SO.sub.2                                          109  Na.sup.+                                                                              n-Propyl Epoxy   S                                                 110  Na.sup.+                                                                              n-Propyl Epoxy   O                                                 111  Na.sup.+                                                                              n-Propyl Epoxy   SO                                                112  Na.sup.+                                                                              n-Propyl Epoxy   SO.sub.2                                          113  Na.sup.+                                                                              n-Butyl  Cl      S                                                 114  Na.sup.+                                                                              n-Butyl  Cl      O                                                 115  Na.sup.+                                                                              n-Butyl  Cl      SO                                                116  Na.sup.+                                                                              n-Butyl  Cl      SO.sub.2                                          117  Na.sup.+                                                                              n-Butyl  Br      S                                                 118  Na.sup.+                                                                              n-Butyl  Br      O                                                 119  Na.sup.+                                                                              n-Butyl  Br      SO                                                120  Na.sup.+                                                                              n-Butyl  Br      SO.sub.2                                          121  Na.sup.+                                                                              n-Butyl  OH      S                                                 122  Na.sup.+                                                                              n-Butyl  OH      O                                                 123  Na.sup.+                                                                              n-Butyl  OH      SO                                                124  Na.sup.+                                                                              n-Butyl  OH      SO.sub.2                                          125  Na.sup.+                                                                              n-Butyl  Epoxy   S                                                 126  Na.sup.+                                                                              n-Butyl  Epoxy   O                                                 127  Na.sup.+                                                                              n-Butyl  Epoxy   SO                                                128  Na.sup.+                                                                              n-Butyl  Epoxy   SO.sub.2                                          129  K.sup.+                                                                               Methyl   Cl      S                                                 130  K.sup.+                                                                               Methyl   Cl      O                                                 131  K.sup.+                                                                               Methyl   Cl      SO                                                132  K.sup.+                                                                               Methyl   Cl      SO.sub.2                                          133  K.sup.+                                                                               Methyl   Br      S                                                 134  K.sup.+                                                                               Methyl   Br      O                                                 135  K.sup.+                                                                               Methyl   Br      SO                                                136  K.sup.+                                                                               Methyl   Br      SO.sub.2                                          137  K.sup.+                                                                               Methyl   OH      S                                                 138  K.sup.+                                                                               Methyl   OH      O                                                 139  K.sup.+                                                                               Methyl   OH      SO                                                140  K.sup.+                                                                               Methyl   OH      SO.sub.2                                          141  K.sup.+                                                                               Methyl   Epoxy   S                                                 142  K.sup.+                                                                               Methyl   Epoxy   O                                                 143  K.sup.+                                                                               Methyl   Epoxy   SO                                                144  K.sup.+                                                                               Ethyl    Epoxy   SO.sub.2                                          145  K.sup.+                                                                               Ethyl    Cl      S                                                 146  K.sup.+                                                                               Ethyl    Cl      O                                                 147  K.sup.+                                                                               Ethyl    Cl      SO                                                148  K.sup.+                                                                               Ethyl    Cl      SO.sub.2                                          149  K.sup.+                                                                               Ethyl    Br      S                                                 150  K.sup.+                                                                               Ethyl    Br      O                                                 151  K.sup.+                                                                               Ethyl    Br      SO                                                152  K.sup.+                                                                               Ethyl    Br      SO.sub.2                                          153  K.sup.+                                                                               Ethyl    OH      S                                                 154  K.sup.+                                                                               Ethyl    OH      O                                                 155  K.sup.+                                                                               Ethyl    OH      SO                                                156  K.sup.+                                                                               Ethyl    OH      SO.sub.2                                          157  K.sup.+                                                                               Ethyl    Epoxy   S                                                 158  K.sup.+                                                                               Ethyl    Epoxy   O                                                 159  K.sup. +                                                                              Ethyl    Epoxy   SO                                                160  K.sup.+                                                                               Ethyl    Epoxy   SO.sub.2                                          161  K.sup.+                                                                               n-Propyl Cl      S                                                 162  K.sup.+                                                                               n-Propyl Cl      O                                                 163  K.sup.+                                                                               n-Propyl Cl      SO                                                164  K.sup.+                                                                               n-Propyl Cl      SO.sub.2                                          165  K.sup.+                                                                               n-Propyl Br      S                                                 166  K.sup.+                                                                               n-Propyl Br      O                                                 167  K.sup.+                                                                               n-Propyl Br      SO                                                168  K.sup.+                                                                               n-Propyl Br      SO.sub.2                                          169  K.sup.+                                                                               n-Propyl OH      S                                                 170  K.sup.+                                                                               n-Propyl OH      O                                                 171  K.sup.+                                                                               n-Propyl OH      SO                                                172  K.sup.+                                                                               n-Propyl OH      SO.sub.2                                          173  K.sup.+                                                                               n-Propyl Epoxy   S                                                 174  K.sup.+                                                                               n-Propyl Epoxy   O                                                 175  K.sup.+                                                                               n-Propyl Epoxy   SO                                                176  K.sup.+                                                                               n-Propyl Epoxy   SO.sub.2                                          177  K.sup.+                                                                               n-Butyl  Cl      S                                                 178  K.sup.+                                                                               n-Butyl  Cl      O                                                 179  K.sup.+                                                                               n-Butyl  Cl      SO                                                180  K.sup.+                                                                               n-Butyl  Cl      SO.sub.2                                          181  K.sup.+                                                                               n-Butyl  Br      S                                                 182  K.sup.+                                                                               n-Butyl  Br      O                                                 183  K.sup.+                                                                               n-Butyl  Br      SO                                                184  K.sup.+                                                                               n-Butyl  Br      SO.sub.2                                          185  K.sup.+                                                                               n-Butyl  OH      S                                                 186  K.sup.+                                                                               n-Butyl  OH      O                                                 187  K.sup.+                                                                               n-Butyl  OH      SO                                                188  K.sup.+                                                                               n-Butyl  OH      SO.sub.2                                          189  K.sup.+                                                                               n-Butyl  Epoxy   S                                                 190  K.sup.+                                                                               n-Butyl  Epoxy   O                                                 191  K.sup.+                                                                               n-Butyl  Epoxy   SO                                                192  K.sup.+                                                                               n-Butyl  Epoxy   SO.sub.2                                          ______________________________________                                    

                                      TABLE 2                                      __________________________________________________________________________      ##STR7##                                                                      No.                                                                               R.sup.1       R.sup.2                                                                             R.sup.3 and R.sup.4                                                                  R.sup.6                                                                            R.sup.7                                                                            B X     .sup.1 H-NMR                       __________________________________________________________________________                                                 data                               193                                                                               H             Ethyl                                                                               Epoxy H   H   O COOCH.sub.3                              194                                                                               H             Ethyl                                                                               Cl    H   H   O COOCH.sub.3                              195                                                                               Trimethylbenzylammonium                                                                      n-Propyl                                                                            Epoxy H   H   O H                                        196                                                                               H             n-Propyl                                                                            Epoxy Methyl                                                                             Methyl                                                                             O H                                        197                                                                               H             n-Propyl                                                                            Cl    H   H   O COOCH.sub.3                              198                                                                               H             n-Propyl                                                                            Br    H   H   O COOCH.sub.3                              __________________________________________________________________________

                                      TABLE 3                                      __________________________________________________________________________      ##STR8##                                                                      No.                                                                               R.sup.1       R.sup.2                                                                             R.sup.3 and R.sup.4                                                                  X     .sup.1 H-NMR data                            __________________________________________________________________________     199                                                                               H             Methyl                                                                              Cl    H                                                  200                                                                               H             Methyl                                                                              Br    H                                                  201                                                                               H             Methyl                                                                              OH    H                                                  202                                                                               H             Methyl                                                                              Epoxy H                                                  203                                                                               H             Ethyl                                                                               Cl    H                                                  204                                                                               H             Ethyl                                                                               Br    H                                                  205                                                                               H             Ethyl                                                                               OH    H                                                  206                                                                               H             Ethyl                                                                               Epoxy H                                                  207                                                                               H             n-Propyl                                                                            Cl    H                                                  208                                                                               H             n-Propyl                                                                            Br    H     1.0(t), 1.7(q), 4.0(s)                       209                                                                               H             n-Propyl                                                                            OH    H                                                  210                                                                               H             n-Propyl                                                                            Epoxy H     1.0(t), 2.5(m), 4.1(m)                       211                                                                               H             n-Butyl                                                                             Cl    H                                                  212                                                                               H             n-Butyl                                                                             Br    H                                                  213                                                                               H             n-Butyl                                                                             OH    H                                                  214                                                                               H             n-Butyl                                                                             Epoxy H                                                  215                                                                               Na.sup.+      Methyl                                                                              Cl    H                                                  216                                                                               Na.sup.+      Methyl                                                                              Br    H                                                  217                                                                               Na.sup.+      Methyl                                                                              OH    H                                                  218                                                                               Na.sup.+      Methyl                                                                              Epoxy H                                                  219                                                                               Na.sup. +     Ethyl                                                                               Cl    H                                                  220                                                                               Na.sup.+      Ethyl                                                                               Br    H                                                  221                                                                               Na.sup.+      Ethyl                                                                               OH    H                                                  222                                                                               Na.sup.+      Ethyl                                                                               Epoxy H                                                  223                                                                               Na.sup.+      n-Propyl                                                                            Cl    H                                                  224                                                                               Na.sup.+      n-Propyl                                                                            Br    H                                                  225                                                                               Na.sup.+      n-Propyl                                                                            OH    H                                                  226                                                                               Na.sup.+      n-Propyl                                                                            Epoxy H                                                  227                                                                               Na.sup.+      n-Butyl                                                                             Cl    H                                                  228                                                                               Na.sup.+      n-Butyl                                                                             Br    H                                                  229                                                                               Na.sup.+      n-Butyl                                                                             OH    H                                                  230                                                                               Na.sup.+      n-Butyl                                                                             Epoxy H                                                  231                                                                               K.sup.+       Methyl                                                                              Cl    H                                                  232                                                                               K.sup.+       Methyl                                                                              Br    H                                                  233                                                                               K.sup.+       Methyl                                                                              OH    H                                                  234                                                                               K.sup.+       Methyl                                                                              Epoxy H                                                  235                                                                               K.sup.+       Ethyl                                                                               Cl    H                                                  236                                                                               K.sup.+       Ethyl                                                                               Br    H                                                  237                                                                               K.sup.+       Ethyl                                                                               OH    H                                                  238                                                                               K.sup.+       Ethyl                                                                               Epoxy H                                                  239                                                                               K.sup.+       n-Propyl                                                                            Cl    H                                                  240                                                                               K.sup.+       n-Propyl                                                                            Br    H                                                  241                                                                               K.sup.+       n-Propyl                                                                            OH    H                                                  242                                                                               K.sup.+       n-Propyl                                                                            Epoxy H                                                  243                                                                               K.sup.+       n-Butyl                                                                             Cl    H                                                  244                                                                               K.sup.+       n-Butyl                                                                             Br    H                                                  245                                                                               K.sup.+       n-Butyl                                                                             OH    H                                                  246                                                                               K.sup.+       n-Butyl                                                                             Epoxy H                                                  247                                                                               H             n-Propyl                                                                            Cl    COOCH.sub.3                                        248                                                                               H             Ethyl                                                                               Cl    COOCH.sub.3                                        249                                                                               Trimethylbenzylammonium                                                                      Ethyl                                                                               Cl    H                                                  250                                                                               Trimethylbenzylammonium                                                                      n-Propyl                                                                            Cl    H                                                  251                                                                               Tetramethylammonium                                                                          Ethyl                                                                               Epoxy H                                                  252                                                                               Tetramethylammonium                                                                          Ethyl                                                                               Cl    COOCH.sub.3                                        __________________________________________________________________________

                                      TABLE 4                                      __________________________________________________________________________      ##STR9##                                                                      No.                                                                               R.sup.2                                                                             R.sup.3 and R.sup.4                                                                  B  R.sup.8     .sup.1 H-NMR data                                 __________________________________________________________________________     253                                                                               Methyl                                                                              Cl    S  Ethyl                                                         254                                                                               Methyl                                                                              Cl    S  Allyl                                                         255                                                                               Methyl                                                                              Cl    S  ( .sub.-- E)-2-Butenyl                                        256                                                                               Methyl                                                                              Cl    S  ( .sub.-- E)-3-Chloro-2-propenyl                              257                                                                               Methyl                                                                              Cl    S  Propargyl                                                     258                                                                               Methyl                                                                              Cl    O  Ethyl                                                         259                                                                               Methyl                                                                              Cl    O  Allyl                                                         260                                                                               Methyl                                                                              Cl    O  ( .sub.-- E)-2-Butenyl                                        261                                                                               Methyl                                                                              Cl    O  ( .sub.-- E)-3-Chloro-2-propenyl                              262                                                                               Methyl                                                                              Cl    O  Propargyl                                                     263                                                                               Methyl                                                                              Cl    SO Ethyl                                                         264                                                                               Methyl                                                                              Cl    SO Allyl                                                         265                                                                               Methyl                                                                              Cl    SO ( .sub.-- E)-2-Butenyl                                        266                                                                               Methyl                                                                              Cl    SO ( .sub.-- E)-3-Chloro-2-propenyl                              267                                                                               Methyl                                                                              Cl    SO Propargyl                                                     268                                                                               Methyl                                                                              Cl    SO.sub.2                                                                          Ethyl                                                         269                                                                               Methyl                                                                              Cl    SO.sub.2                                                                          Allyl                                                         270                                                                               Methyl                                                                              Cl    SO.sub.2                                                                          ( .sub.-- E)-2-Butenyl                                        271                                                                               Methyl                                                                              Cl    SO.sub.2                                                                          ( .sub.-- E)-3-Chloro-2-propenyl                              272                                                                               Methyl                                                                              Cl    SO.sub.2                                                                          Propargyl                                                     273                                                                               Methyl                                                                              Br    S  Ethyl                                                         274                                                                               Methyl                                                                              Br    S  Allyl                                                         275                                                                               Methyl                                                                              Br    S  ( .sub.-- E)-2-Butenyl                                        276                                                                               Methyl                                                                              Br    S  ( .sub.-- E)-3-Chloro-2-propenyl                              277                                                                               Methyl                                                                              Br    S  Propargyl                                                     278                                                                               Methyl                                                                              Br    O  Ethyl                                                         279                                                                               Methyl                                                                              Br    O  Allyl                                                         280                                                                               Methyl                                                                              Br    O  ( .sub.-- E)-2-Butenyl                                        281                                                                               Methyl                                                                              Br    O  ( .sub.-- E)-3-Chloro-2-propenyl                              282                                                                               Methyl                                                                              Br    O  Propargyl                                                     283                                                                               Methyl                                                                              Br    SO Ethyl                                                         284                                                                               Methyl                                                                              Br    SO Allyl                                                         285                                                                               Methyl                                                                              Br    SO ( .sub.-- E)-2-Butenyl                                        286                                                                               Methyl                                                                              Br    SO ( .sub.-- E)-3-Chloro-2-propenyl                              287                                                                               Methyl                                                                              Br    SO Propargyl                                                     288                                                                               Methyl                                                                              Br    SO.sub.2                                                                          Ethyl                                                         289                                                                               Methyl                                                                              Br    SO.sub.2                                                                          Allyl                                                         290                                                                               Methyl                                                                              Br    SO.sub.2                                                                          ( .sub.-- E)-2-Butenyl                                        291                                                                               Methyl                                                                              Br    SO.sub.2                                                                          ( .sub.-- E)-3-Chloro-2-propenyl                              292                                                                               Methyl                                                                              Br    SO.sub.2                                                                          Propargyl                                                     293                                                                               Methyl                                                                              OH    S  Ethyl                                                         294                                                                               Methyl                                                                              OH    S  Allyl                                                         295                                                                               Methyl                                                                              OH    S  ( .sub.-- E)-2-Butenyl                                        296                                                                               Methyl                                                                              OH    S  ( .sub.-- E)-3-Chloro-2-propenyl                              297                                                                               Methyl                                                                              OH    S  Propargyl                                                     298                                                                               Methyl                                                                              OH    O  Ethyl                                                         299                                                                               Methyl                                                                              OH    O  Allyl                                                         300                                                                               Methyl                                                                              OH    O  ( .sub.-- E)-2-Butenyl                                        301                                                                               Methyl                                                                              OH    O  ( .sub.-- E)-3-Chloro-2-propenyl                              302                                                                               Methyl                                                                              OH    O  Propargyl                                                     303                                                                               Methyl                                                                              OH    SO Ethyl                                                         304                                                                               Methyl                                                                              OH    SO Allyl                                                         305                                                                               Methyl                                                                              OH    SO ( .sub.-- E)-2-Butenyl                                        306                                                                               Methyl                                                                              OH    SO ( .sub.-- E)-3-Chloro-2-propenyl                              307                                                                               Methyl                                                                              OH    SO Propargyl                                                     308                                                                               Methyl                                                                              OH    SO.sub.2                                                                          Ethyl                                                         309                                                                               Methyl                                                                              OH    SO.sub.2                                                                          Allyl                                                         310                                                                               Methyl                                                                              OH    SO.sub.2                                                                          ( .sub.-- E)-2-Butenyl                                        311                                                                               Methyl                                                                              OH    SO.sub.2                                                                          ( .sub.-- E)-3-Chloro-2-propenyl                              312                                                                               Methyl                                                                              OH    SO.sub.2                                                                          Propargyl                                                     313                                                                               Methyl                                                                              Epoxy S  Ethyl                                                         314                                                                               Methyl                                                                              Epoxy S  Allyl                                                         315                                                                               Methyl                                                                              Epoxy S  ( .sub.-- E)-2-Butenyl                                        316                                                                               Methyl                                                                              Epoxy S  ( .sub.-- E)-3-Chloro-2-propenyl                              317                                                                               Methyl                                                                              Epoxy S  Propargyl                                                     318                                                                               Methyl                                                                              Epoxy O  Ethyl                                                         319                                                                               Methyl                                                                              Epoxy O  Allyl                                                         320                                                                               Methyl                                                                              Epoxy O  ( .sub.-- E)-2-Butenyl                                        321                                                                               Methyl                                                                              Epoxy O  ( .sub.-- E)-3-Chloro-2-propenyl                              322                                                                               Methyl                                                                              Epoxy O  Propargyl                                                     323                                                                               Methyl                                                                              Epoxy SO Ethyl                                                         324                                                                               Methyl                                                                              Epoxy SO Allyl                                                         325                                                                               Methyl                                                                              Epoxy SO ( .sub.-- E)-2-Butenyl                                        326                                                                               Methyl                                                                              Epoxy SO ( .sub.-- E)-3-Chloro-2-propenyl                              327                                                                               Methyl                                                                              Epoxy SO Propargyl                                                     328                                                                               Methyl                                                                              Epoxy SO.sub.2                                                                          Ethyl                                                         329                                                                               Methyl                                                                              Epoxy SO.sub.2                                                                          Allyl                                                         330                                                                               Methyl                                                                              Epoxy SO.sub.2                                                                          ( .sub.-- E)-2-Butenyl                                        331                                                                               Methyl                                                                              Epoxy SO.sub.2                                                                          ( .sub.-- E)-3-Chloro-2-propenyl                              332                                                                               Methyl                                                                              Epoxy SO.sub.2                                                                          Propargyl                                                     333                                                                               Ethyl                                                                               Cl    S  Ethyl                                                         334                                                                               Ethyl                                                                               Cl    S  Allyl                                                         335                                                                               Ethyl                                                                               Cl    S  ( .sub.-- E)-2-Butenyl                                        336                                                                               Ethyl                                                                               Cl    S  ( .sub.-- E)-3-Chloro-2-propenyl                              337                                                                               Ethyl                                                                               Cl    S  Propargyl                                                     338                                                                               Ethyl                                                                               Cl    O  Ethyl                                                         339                                                                               Ethyl                                                                               Cl    O  Allyl                                                         340                                                                               Ethyl                                                                               Cl    O  ( .sub.-- E)-2-Butenyl                                        341                                                                               Ethyl                                                                               Cl    O  ( .sub.-- E)-3-Chloro-2-propenyl                              342                                                                               Ethyl                                                                               Cl    O  Propargyl                                                     343                                                                               Ethyl                                                                               Cl    SO Ethyl                                                         344                                                                               Ethyl                                                                               Cl    SO Allyl                                                         345                                                                               Ethyl                                                                               Cl    SO ( .sub.-- E)-2-Butenyl                                        346                                                                               Ethyl                                                                               Cl    SO ( .sub.-- E)-3-Chloro-2-propenyl                              347                                                                               Ethyl                                                                               Cl    SO Propargyl                                                     348                                                                               Ethyl                                                                               Cl    SO.sub.2                                                                          Ethyl                                                         349                                                                               Ethyl                                                                               Cl    SO.sub.2                                                                          Allyl                                                         350                                                                               Ethyl                                                                               Cl    SO.sub.2                                                                          ( .sub.-- E)-2-Butenyl                                        351                                                                               Ethyl                                                                               Cl    SO.sub.2                                                                          ( .sub.-- E)-3-Chloro-2-propenyl                              352                                                                               Ethyl                                                                               Cl    SO.sub.2                                                                          Propargyl                                                     353                                                                               Ethyl                                                                               Br    S  Ethyl                                                         354                                                                               Ethyl                                                                               Br    S  Allyl                                                         355                                                                               Ethyl                                                                               Br    S  ( .sub.-- E)-2-Butenyl                                        356                                                                               Ethyl                                                                               Br    S  ( .sub.-- E)-3-Chloro-2-propenyl                              357                                                                               Ethyl                                                                               Br    S  Propargyl                                                     358                                                                               Ethyl                                                                               Br    O  Ethyl                                                         359                                                                               Ethyl                                                                               Br    O  Allyl                                                         360                                                                               Ethyl                                                                               Br    O  ( .sub.-- E)-2-Butenyl                                        361                                                                               Ethyl                                                                               Br    O  ( .sub.-- E)-3-Chloro-2-propenyl                              362                                                                               Ethyl                                                                               Br    O  Propargyl                                                     363                                                                               Ethyl                                                                               Br    SO Ethyl                                                         364                                                                               Ethyl                                                                               Br    SO Allyl                                                         365                                                                               Ethyl                                                                               Br    SO ( .sub.-- E)-2-Butenyl                                        366                                                                               Ethyl                                                                               Br    SO ( .sub.-- E)-3-Chloro-2-propenyl                              367                                                                               Ethyl                                                                               Br    SO Propargyl                                                     368                                                                               Ethyl                                                                               Br    SO.sub.2                                                                          Ethyl                                                         369                                                                               Ethyl                                                                               Br    SO.sub.2                                                                          Allyl                                                         370                                                                               Ethyl                                                                               Br    SO.sub.2                                                                          ( .sub.-- E)-2-Butenyl                                        371                                                                               Ethyl                                                                               Br    SO.sub.2                                                                          ( .sub.-- E)-3-Chloro-2-propenyl                              372                                                                               Ethyl                                                                               Br    SO.sub.2                                                                          Propargyl                                                     373                                                                               Ethyl                                                                               OH    S  Ethyl                                                         374                                                                               Ethyl                                                                               OH    S  Allyl                                                         375                                                                               Ethyl                                                                               OH    S  ( .sub.-- E)-2-Butenyl                                        376                                                                               Ethyl                                                                               OH    S  ( .sub.-- E)-3-Chloro-2-propenyl                              377                                                                               Ethyl                                                                               OH    S  Propargyl                                                     378                                                                               Ethyl                                                                               OH    O  Ethyl                                                         379                                                                               Ethyl                                                                               OH    O  Allyl                                                         380                                                                               Ethyl                                                                               OH    O  ( .sub.-- E)-2-Butenyl                                        381                                                                               Ethyl                                                                               OH    O  ( .sub.-- E)-3-Chloro-2-propenyl                              382                                                                               Ethyl                                                                               OH    O  Propargyl                                                     383                                                                               Ethyl                                                                               OH    SO Ethyl                                                         384                                                                               Ethyl                                                                               OH    SO Allyl                                                         385                                                                               Ethyl                                                                               OH    SO ( .sub.-- E)-2-Butenyl                                        386                                                                               Ethyl                                                                               OH    SO ( .sub.-- E)-3-Chloro-2-propenyl                              387                                                                               Ethyl                                                                               OH    SO Propargyl                                                     388                                                                               Ethyl                                                                               OH    SO.sub.2                                                                          Ethyl                                                         389                                                                               Ethyl                                                                               OH    SO.sub.2                                                                          Allyl                                                         390                                                                               Ethyl                                                                               OH    SO.sub.2                                                                          ( .sub.-- E)-2-Butenyl                                        391                                                                               Ethyl                                                                               OH    SO.sub.2                                                                          ( .sub.-- E)-3-Chloro-2-propenyl                              392                                                                               Ethyl                                                                               OH    SO.sub.2                                                                          Propargyl                                                     393                                                                               Ethyl                                                                               Epoxy S  Ethyl                                                         394                                                                               Ethyl                                                                               Epoxy S  Allyl                                                         395                                                                               Ethyl                                                                               Epoxy S  ( .sub.-- E)-2-Butenyl                                        396                                                                               Ethyl                                                                               Epoxy S  ( .sub.-- E)-3-Chloro-2-propenyl                              397                                                                               Ethyl                                                                               Epoxy S  Propargyl                                                     398                                                                               Ethyl                                                                               Epoxy O  Ethyl       1.3(t), 2.5(m), 3.3(s)                            399                                                                               Ethyl                                                                               Epoxy O  Allyl       1.1(t), 3.5(m), 4.6(d)                            400                                                                               Ethyl                                                                               Epoxy O  ( .sub.-- E)-2-Butenyl                                        401                                                                               Ethyl                                                                               Epoxy O  ( .sub.-- E)-3-Chloro-2-propenyl                                                           2.0(m), 3.5(m), 6.35(d)                           402                                                                               Ethyl                                                                               Epoxy O  Propargyl                                                     403                                                                               Ethyl                                                                               Epoxy SO Ethyl                                                         404                                                                               Ethyl                                                                               Epoxy SO Allyl                                                         405                                                                               Ethyl                                                                               Epoxy SO ( .sub.-- E)-2-Butenyl                                        406                                                                               Ethyl                                                                               Epoxy SO ( .sub.-- E)-3-Chloro-2-propenyl                              407                                                                               Ethyl                                                                               Epoxy SO Propargyl                                                     408                                                                               Ethyl                                                                               Epoxy SO.sub.2                                                                          Ethyl                                                         409                                                                               Ethyl                                                                               Epoxy SO.sub.2                                                                          Allyl                                                         410                                                                               Ethyl                                                                               Epoxy SO.sub.2                                                                          ( .sub.-- E)-2-Butenyl                                        411                                                                               Ethyl                                                                               Epoxy SO.sub.2                                                                          ( .sub.-- E)-3-Chloro-2-propenyl                              412                                                                               Ethyl                                                                               Epoxy SO.sub.2                                                                          Propargyl                                                     413                                                                               n-Propyl                                                                            Cl    S  Ethyl                                                         414                                                                               n-Propyl                                                                            Cl    S  Allyl                                                         415                                                                               n-Propyl                                                                            Cl    S  ( .sub.-- E)-2-Butenyl                                        416                                                                               n-Propyl                                                                            Cl    S  ( .sub.-- E)-3-Chloro-2-propenyl                              417                                                                               n-Propyl                                                                            Cl    S  Propargyl                                                     418                                                                               n-Propyl                                                                            Cl    O  Ethyl       1.3(t), 1.6(q), 4.4(s)                            419                                                                               n-Propyl                                                                            Cl    O  Allyl                                                         420                                                                               n-Propyl                                                                            Cl    O  ( .sub.-- E)-2-Butenyl                                        421                                                                               n-Propyl                                                                            Cl    O  ( .sub.-- E)-3-Chloro-2-propenyl                                                           1.0(t), 3.9(m), 4.5(d)                            422                                                                               n-Propyl                                                                            Cl    O  Propargyl                                                     423                                                                               n-Propyl                                                                            Cl    SO Ethyl                                                         424                                                                               n-Propyl                                                                            Cl    SO Allyl                                                         425                                                                               n-Propyl                                                                            Cl    SO ( .sub.-- E)-2-Butenyl                                        426                                                                               n-Propyl                                                                            Cl    SO ( .sub.-- E)-3-Chloro-2-propenyl                              427                                                                               n-Propyl                                                                            Cl    SO Propargyl                                                     428                                                                               n-Propyl                                                                            Cl    SO.sub.2                                                                          Ethyl                                                         429                                                                               n-Propyl                                                                            Cl    SO.sub.2                                                                          Allyl                                                         430                                                                               n-Propyl                                                                            Cl    SO.sub.2                                                                          ( .sub.-- E)-2-Butenyl                                        431                                                                               n-Propyl                                                                            Cl    SO.sub.2                                                                          ( .sub.-- E)-3-Chloro-2-propenyl                              432                                                                               n-Propyl                                                                            Cl    SO.sub.2                                                                          Propargyl                                                     433                                                                               n-Propyl                                                                            Br    S  Ethyl                                                         434                                                                               n-Propyl                                                                            Br    S  Allyl                                                         435                                                                               n-Propyl                                                                            Br    S  ( .sub.-- E)-2-Butenyl                                        436                                                                               n-Propyl                                                                            Br    S  ( .sub.-- E)-3-Chloro-2-propenyl                              437                                                                               n-Propyl                                                                            Br    S  Propargyl                                                     438                                                                               n-Propyl                                                                            Br    O  Ethyl       1.3(t), 3.9(m), 4.65(s)                           439                                                                               n-Propyl                                                                            Br    O  Allyl       1.9(d), 4.5(d), 4.6(s)                            440                                                                               n-Propyl                                                                            Br    O  ( .sub.-- E)-2-Butenyl                                                                     0.95(t), 1.8(d), 4.6(s)                           441                                                                               n-Propyl                                                                            Br    O  ( .sub.-- E)-3-Chloro-2-propenyl                                                           0.95(t), 1.5(q), 6.3(d)                           442                                                                               n-Propyl                                                                            Br    O  Propargyl                                                     443                                                                               n-Propyl                                                                            Br    SO Ethyl                                                         444                                                                               n-Propyl                                                                            Br    SO Allyl                                                         445                                                                               n-Propyl                                                                            Br    SO ( .sub.-- E)-2-Butenyl                                        446                                                                               n-Propyl                                                                            Br    SO ( .sub.-- E)-3-Chloro-2-propenyl                              447                                                                               n-Propyl                                                                            Br    SO Propargyl                                                     448                                                                               n-Propyl                                                                            Br    SO.sub.2                                                                          Ethyl                                                         449                                                                               n-Propyl                                                                            Br    SO.sub.2                                                                          Allyl                                                         450                                                                               n-Propyl                                                                            Br    SO.sub.2                                                                          ( .sub.-- E)-2-Butenyl                                        451                                                                               n-Propyl                                                                            Br    SO.sub.2                                                                          ( .sub.-- E)-3-Chloro-2-propenyl                              452                                                                               n-Propyl                                                                            Br    SO.sub.2                                                                          Propargyl                                                     453                                                                               n-Propyl                                                                            OH    S  Ethyl                                                         454                                                                               n-Propyl                                                                            OH    S  Allyl                                                         455                                                                               n-Propyl                                                                            OH    S  ( .sub.-- E)-2-Butenyl                                        456                                                                               n-Propyl                                                                            OH    S  ( .sub.-- E)-3-Chloro-2-propenyl                              457                                                                               n-Propyl                                                                            OH    S  Propargyl                                                     458                                                                               n-Propyl                                                                            OH    O  Ethyl       1.0(t), 2.6(m), 4.1(q)                            459                                                                               n-Propyl                                                                            OH    O  Allyl                                                         460                                                                               n-Propyl                                                                            OH    O  ( .sub.-- E)-2-Butenyl                                        461                                                                               n-Propyl                                                                            OH    O  ( .sub.-- E)-3-Chloro-2-propenyl                              462                                                                               n-Propyl                                                                            OH    O  Propargyl                                                     463                                                                               n-Propyl                                                                            OH    SO Ethyl                                                         464                                                                               n-Propyl                                                                            OH    SO Allyl                                                         465                                                                               n-Propyl                                                                            OH    SO ( .sub.-- E)-2-Butenyl                                        466                                                                               n-Propyl                                                                            OH    SO ( .sub.-- E)-3-Chloro-2-propenyl                              467                                                                               n-Propyl                                                                            OH    SO Propargyl                                                     468                                                                               n-Propyl                                                                            OH    SO.sub.2                                                                          Ethyl                                                         469                                                                               n-Propyl                                                                            OH    SO.sub.2                                                                          Allyl                                                         470                                                                               n-Propyl                                                                            OH    SO.sub.2                                                                          ( .sub.-- E)-2-Butenyl                                        471                                                                               n-Propyl                                                                            OH    SO.sub.2                                                                          ( .sub.-- E)-3-Chloro-2-propenyl                              472                                                                               n-Propyl                                                                            OH    SO.sub.2                                                                          Propargyl                                                     473                                                                               n-Propyl                                                                            Epoxy S  Ethyl                                                         474                                                                               n-Propyl                                                                            Epoxy S  Allyl                                                         475                                                                               n-Propyl                                                                            Epoxy S  ( .sub.-- E)-2-Butenyl                                        476                                                                               n-Propyl                                                                            Epoxy S  ( .sub.-- E)-3-Chloro-2-propenyl                              477                                                                               n-Propyl                                                                            Epoxy S  Propargyl                                                     478                                                                               n-Propyl                                                                            Epoxy O  Ethyl       1.35(t), 2.0(m), 3.3(s)                           479                                                                               n-Propyl                                                                            Epoxy O  Allyl                                                         480                                                                               n-Propyl                                                                            Epoxy O  ( .sub.-- E)-2-Butenyl                                                                     0.95(t), 1.5(m), 3.3(s)                           481                                                                               n-Propyl                                                                            Epoxy O  ( .sub.-- E)-3-Chloro-2-propenyl                              482                                                                               n-Propyl                                                                            Epoxy O  Propargyl                                                     483                                                                               n-Propyl                                                                            Epoxy SO Ethyl                                                         484                                                                               n-Propyl                                                                            Epoxy SO Allyl                                                         485                                                                               n-Propyl                                                                            Epoxy SO ( .sub.-- E)-2-Butenyl                                        486                                                                               n-Propyl                                                                            Epoxy SO ( .sub.-- E)-3-Chloro-2-propenyl                              487                                                                               n-Propyl                                                                            Epoxy SO Propargyl                                                     488                                                                               n-Propyl                                                                            Epoxy SO.sub.2                                                                          Ethyl                                                         489                                                                               n-Propyl                                                                            Epoxy SO.sub.2                                                                          Allyl                                                         490                                                                               n-Propyl                                                                            Epoxy SO.sub.2                                                                          ( .sub.-- E)-2-Butenyl                                        491                                                                               n-Propyl                                                                            Epoxy SO.sub.2                                                                          ( .sub.-- E)-3-Chloro-2-propenyl                              492                                                                               n-Propyl                                                                            Epoxy SO.sub.2                                                                          Propargyl                                                     493                                                                               n-Butyl                                                                             Cl    S  Ethyl                                                         494                                                                               n-Butyl                                                                             Cl    S  Allyl                                                         495                                                                               n-Butyl                                                                             Cl    S  ( .sub.-- E)-2-Butenyl                                        496                                                                               n-Butyl                                                                             Cl    S  ( .sub.-- E)-3-Chloro-2-propenyl                              497                                                                               n-Butyl                                                                             Cl    S  Propargyl                                                     498                                                                               n-Butyl                                                                             Cl    O  Ethyl                                                         499                                                                               n-Butyl                                                                             Cl    O  Allyl                                                         500                                                                               n-Butyl                                                                             Cl    O  (  .sub.-- E)-2-Butenyl                                       501                                                                               n-Butyl                                                                             Cl    O  ( .sub.-- E)-3-Chloro-2-propenyl                              502                                                                               n-Butyl                                                                             Cl    O  Propargyl                                                     503                                                                               n-Butyl                                                                             Cl    SO Ethyl                                                         504                                                                               n-Butyl                                                                             Cl    SO Allyl                                                         505                                                                               n-Butyl                                                                             Cl    SO ( .sub.-- E)-2-Butenyl                                        506                                                                               n-Butyl                                                                             Cl    SO ( .sub.-- E)-3-Chloro-2-propenyl                              507                                                                               n-Butyl                                                                             Cl    SO Propargyl                                                     508                                                                               n-Butyl                                                                             Cl    SO.sub.2                                                                          Ethyl                                                         509                                                                               n-Butyl                                                                             Cl    SO.sub.2                                                                          Allyl                                                         510                                                                               n-Butyl                                                                             Cl    SO.sub.2                                                                          ( .sub.-- E)-2-Butenyl                                        511                                                                               n-Butyl                                                                             Cl    SO.sub.2                                                                          ( .sub.-- E)-3-Chloro-2-propenyl                              512                                                                               n-Butyl                                                                             Cl    SO.sub.2                                                                          Propargyl                                                     513                                                                               n-Butyl                                                                             Br    S  Ethyl                                                         514                                                                               n-Butyl                                                                             Br    S  Allyl                                                         515                                                                               n-Butyl                                                                             Br    S  ( .sub.-- E)-2-Butenyl                                        516                                                                               n-Butyl                                                                             Br    S  ( .sub.-- E)-3-Chloro-2-propenyl                              517                                                                               n-Butyl                                                                             Br    S  Propargyl                                                     518                                                                               n-Butyl                                                                             Br    O  Ethyl                                                         519                                                                               n-Butyl                                                                             Br    O  Allyl                                                         520                                                                               n-Butyl                                                                             Br    O  ( .sub.-- E)-2-Butenyl                                        521                                                                               n-Butyl                                                                             Br    O  ( .sub.-- E)-3-Chloro-2-propenyl                              522                                                                               n-Butyl                                                                             Br    O  Propargyl                                                     523                                                                               n-Butyl                                                                             Br    SO Ethyl                                                         524                                                                               n-Butyl                                                                             Br    SO Allyl                                                         525                                                                               n-Butyl                                                                             Br    SO ( .sub.-- E)-2-Butenyl                                        526                                                                               n-Butyl                                                                             Br    SO ( .sub.-- E)-3-Chloro-2-propenyl                              527                                                                               n-Butyl                                                                             Br    SO Propargyl                                                     528                                                                               n-Butyl                                                                             Br    SO.sub.2                                                                          Ethyl                                                         529                                                                               n-Butyl                                                                             Br    SO.sub.2                                                                          Allyl                                                         530                                                                               n-Butyl                                                                             Br    SO.sub.2                                                                          ( .sub.-- E)-2-Butenyl                                        531                                                                               n-Butyl                                                                             Br    SO.sub.2                                                                          ( .sub.-- E)-3-Chloro-2-propenyl                              532                                                                               n-Butyl                                                                             Br    SO.sub.2                                                                          Propargyl                                                     533                                                                               n-Butyl                                                                             OH    S  Ethyl                                                         534                                                                               n-Butyl                                                                             OH    S  Allyl                                                         535                                                                               n-Butyl                                                                             OH    S  ( .sub.-- E)-2-Butenyl                                        536                                                                               n-Butyl                                                                             OH    S  ( .sub.-- E)-3-Chloro-2-propenyl                              537                                                                               n-Butyl                                                                             OH    S  Propargyl                                                     538                                                                               n-Butyl                                                                             OH    O  Ethyl                                                         539                                                                               n-Butyl                                                                             OH    O  Allyl                                                         540                                                                               n-Butyl                                                                             OH    O  ( .sub.-- E)-2-Butenyl                                        541                                                                               n-Butyl                                                                             OH    O  ( .sub.-- E)-3-Chloro-2-propenyl                              542                                                                               n-Butyl                                                                             OH    O  Propargyl                                                     543                                                                               n-Butyl                                                                             OH    SO Ethyl                                                         544                                                                               n-Butyl                                                                             OH    SO Allyl                                                         545                                                                               n-Butyl                                                                             OH    SO ( .sub.-- E)-2-Butenyl                                        546                                                                               n-Butyl                                                                             OH    SO ( .sub.-- E)-3-Chloro-2-propenyl                              547                                                                               n-Butyl                                                                             OH    SO Propargyl                                                     548                                                                               n-Butyl                                                                             OH    SO.sub.2                                                                          Ethyl                                                         549                                                                               n-Butyl                                                                             OH    SO.sub.2                                                                          Allyl                                                         550                                                                               n-Butyl                                                                             OH    SO.sub.2                                                                          ( .sub.-- E)-2-Butenyl                                        551                                                                               n-Butyl                                                                             OH    SO.sub.2                                                                          ( .sub.--  E)-3-Chloro-2-propenyl                             552                                                                               n-Butyl                                                                             OH    SO.sub.2                                                                          Propargyl                                                     553                                                                               n-Butyl                                                                             Epoxy S  Ethyl                                                         554                                                                               n-Butyl                                                                             Epoxy S  Allyl                                                         555                                                                               n-Butyl                                                                             Epoxy S  ( .sub.-- E)-2-Butenyl                                        556                                                                               n-Butyl                                                                             Epoxy S  ( .sub.-- E)-3-Chloro-2-propenyl                              557                                                                               n-Butyl                                                                             Epoxy S  Propargyl                                                     558                                                                               n-Butyl                                                                             Epoxy O  Ethyl                                                         559                                                                               n-Butyl                                                                             Epoxy O  Allyl                                                         560                                                                               n-Butyl                                                                             Epoxy O  ( .sub.-- E)-2-Butenyl                                        561                                                                               n-Butyl                                                                             Epoxy O  ( .sub.-- E)-3-Chloro-2-propenyl                              562                                                                               n-Butyl                                                                             Epoxy O  Propargyl                                                     563                                                                               n-Butyl                                                                             Epoxy SO Ethyl                                                         564                                                                               n-Butyl                                                                             Epoxy SO Allyl                                                         565                                                                               n-Butyl                                                                             Epoxy SO ( .sub.-- E)-2-Butenyl                                        566                                                                               n-Butyl                                                                             Epoxy SO ( .sub.-- E)-3-Chloro-2-propenyl                              567                                                                               n-Butyl                                                                             Epoxy SO Propargyl                                                     568                                                                               n-Butyl                                                                             Epoxy SO.sub.2                                                                          Ethyl                                                         569                                                                               n-Butyl                                                                             Epoxy SO.sub.2                                                                          Allyl                                                         570                                                                               n-Butyl                                                                             Epoxy SO.sub.2                                                                          ( .sub.-- E)-2-Butenyl                                        571                                                                               n-Butyl                                                                             Epoxy SO.sub.2                                                                          ( .sub.-- E)-3-Chloro-2-propenyl                              572                                                                               n-Butyl                                                                             Epoxy SO.sub.2                                                                          Propargyl                                                     __________________________________________________________________________

                                      TABLE 5                                      __________________________________________________________________________      ##STR10##                                                                     No.                                                                               R.sup.1                                                                             R.sup.2                                                                             R.sup.3                                                                              R.sup.4    R.sup.6 and R.sup.7                                                                  R.sup.8                                                                              .sup.1 H-NMR data                    __________________________________________________________________________     573                                                                               H    n-Propyl                                                                            OH    Dimethylamino                                                                             H     Ethyl                                      574                                                                               H    n-Propyl                                                                            OH    Methylthio H     Ethyl                                      575                                                                               H    n-Propyl                                                                            OH    Ethylthio  H     Ethyl                                      576                                                                               H    n-Propyl                                                                            OH    Methylcarbonylthio                                                                        H     Ethyl                                      577                                                                               H    n-Propal                                                                            OH    Carboxylmethylthio                                                                        H     Ethyl                                      578                                                                               H    n-Propyl                                                                            H     Methylthio H     Ethyl                                      579                                                                               H    n-Propyl                                                                            H     Ethylthio  H     Ethyl                                      580                                                                               H    n-Propyl                                                                            H     Methylcarbonylthio                                                                        H     Ethyl                                      581                                                                               H    n-Propyl                                                                            H     Carboxylmethylthio                                                                        H     Ethyl                                      582                                                                               Benzoyl                                                                             n-Propyl                                                                            OH    Methylthio H     Ethyl                                      583                                                                               H    Ethyl                                                                               H     Methylcarbonylthio                                                                        H     Ethyl                                      584                                                                               H    Ethyl                                                                               H     Methylcarbonylthio                                                                        H     Allyl                                      585                                                                               H    Ethyl                                                                               H     Methylcarbonylthio                                                                        H     Propargyl                                  586                                                                               H    Methyl                                                                              H     Methylcarbonylthio                                                                        H     Ethyl                                      587                                                                               H    Methyl                                                                              H     Methylcarbonylthio                                                                        H     Allyl                                      588                                                                               Benzoyl                                                                             n-Propyl                                                                            R.sup.3 and R.sup.4 = Epoxy                                                                     H     Ethyl                                      589                                                                               Stearoyl                                                                            n-Propyl                                                                            R.sup.3 and R.sup.4 = Epoxy                                                                     H     Ethyl                                      590                                                                               H    n-Propyl                                                                            Methylthio                                                                           OH         Methyl                                                                               Ethyl                                      591                                                                               H    n-Propyl                                                                            Ethylthio                                                                            OH         Methyl                                                                               Ethyl                                      672                                                                               H    n-Propyl                                                                            R.sup.3 and R.sup.4 = Epoxy                                                                     Methyl                                                                               Ethyl 0.96(t), 3.91(q),                                                              4.09(q)                              __________________________________________________________________________

                                      TABLE 6                                      __________________________________________________________________________      ##STR11##                                                                     No.                                                                               R.sup.2                                                                             R.sup.3 and R.sup.4                                                                  R.sup.8     .sup.1 H-NMR data                                    __________________________________________________________________________     592                                                                               Methyl                                                                              Cl    Ethyl                                                            593                                                                               Methyl                                                                              Cl    Allyl                                                            594                                                                               Methyl                                                                              Cl    ( .sub.-- E)-2-Butenyl                                           595                                                                               Methyl                                                                              Cl    ( .sub.-- E)-3-Chloro-2-propenyl                                 596                                                                               Methyl                                                                              Cl    Propargyl                                                        597                                                                               Methyl                                                                              Br    Ethyl                                                            598                                                                               Methyl                                                                              Br    Allyl                                                            599                                                                               Methyl                                                                              Br    ( .sub.-- E)-2-Butenyl                                           600                                                                               Methyl                                                                              Br    ( .sub.-- E)-3-Chloro-2-propenyl                                 601                                                                               Methyl                                                                              Br    Propargyl                                                        602                                                                               Methyl                                                                              OH    Ethyl                                                            603                                                                               Methyl                                                                              OH    Allyl                                                            604                                                                               Methyl                                                                              OH    ( .sub.-- E)-2-Butenyl                                           605                                                                               Methyl                                                                              OH    ( .sub.-- E)-3-Chloro-2-propenyl                                 606                                                                               Methyl                                                                              OH    Propargyl                                                        607                                                                               Methyl                                                                              Epoxy Ethyl                                                            608                                                                               Methyl                                                                              Epoxy Allyl                                                            609                                                                               Methyl                                                                              Epoxy ( .sub.-- E)-2-Butenyl                                           610                                                                               Methyl                                                                              Epoxy ( .sub.-- E)-3-Chloro-2-propenyl                                 611                                                                               Methyl                                                                              Epoxy Propargyl                                                        612                                                                               Ethyl                                                                               Cl    Ethyl                                                            613                                                                               Ethyl                                                                               Cl    Allyl                                                            614                                                                               Ethyl                                                                               Cl    ( .sub.-- E)-2-Butenyl                                           615                                                                               Ethyl                                                                               Cl    ( .sub.-- E)-3-Chloro-2-propenyl                                 616                                                                               Ethyl                                                                               Cl    Propargyl                                                        617                                                                               Ethyl                                                                               Br    Ethyl                                                            618                                                                               Ethyl                                                                               Br    Allyl                                                            619                                                                               Ethyl                                                                               Br    ( .sub.-- E)-2-Butenyl                                           620                                                                               Ethyl                                                                               Br    ( .sub.-- E)-3-Chloro-2-propenyl                                 621                                                                               Ethyl                                                                               Br    Propargyl                                                        622                                                                               Ethyl                                                                               OH    Ethyl                                                            623                                                                               Ethyl                                                                               OH    Allyl                                                            624                                                                               Ethyl                                                                               OH    ( .sub.-- E)-2-Butenyl                                           625                                                                               Ethyl                                                                               OH    ( .sub.-- E)-3-Chloro-2-propenyl                                 626                                                                               Ethyl                                                                               OH    Propargyl                                                        627                                                                               Ethyl                                                                               Epoxy Ethyl                                                            628                                                                               Ethyl                                                                               Epoxy Allyl                                                            629                                                                               Ethyl                                                                               Epoxy ( .sub.-- E)-2-Butenyl                                           630                                                                               Ethyl                                                                               Epoxy ( .sub.-- E)-3-Chloro-2-propenyl                                 631                                                                               Ethyl                                                                               Epoxy Propargyl                                                        632                                                                               n-Propyl                                                                            Cl    Ethyl                                                            633                                                                               n-Propyl                                                                            Cl    Allyl                                                            634                                                                               n-Propyl                                                                            Cl    ( .sub.-- E)-2-Butenyl                                           635                                                                               n-Propyl                                                                            Cl    ( .sub.-- E)-3-Chloro-2-propenyl                                 636                                                                               n-Propyl                                                                            Cl    Propargyl                                                        637                                                                               n-Propyl                                                                            Br    Ethyl       1.6(q), 2.6(m), 4.1(q)                               638                                                                               n-Propyl                                                                            Br    Allyl       1.0(t), 3.9(m), 5.4(m)                               639                                                                               n-Propyl                                                                            Br    ( .sub.-- E)-2-Butenyl                                                                     1.0(t), 1.7(m), 2.9(m)                               640                                                                               n-Propyl                                                                            Br    ( .sub.-- E)-3-Chloro-2-propenyl                                                           1.5(q), 2.9(t), 4.0(s)                               641                                                                               n-Propyl                                                                            Br    Propargyl                                                        642                                                                               n-Propyl                                                                            OH    Ethyl                                                            643                                                                               n-Propyl                                                                            OH    Allyl                                                            644                                                                               n-Propyl                                                                            OH    ( .sub.-- E)-2-Butenyl                                           645                                                                               n-Propyl                                                                            OH    ( .sub.-- E)-3-Chloro-2-propenyl                                 646                                                                               n-Propyl                                                                            OH    Propargyl                                                        647                                                                               n-Propyl                                                                            Epoxy Ethyl       1.3(t), 2.3(m), 3.1(s)                               648                                                                               n-Propyl                                                                            Epoxy Allyl       0.95(t), 3.1(s), 4.5(d)                              649                                                                               n-Propyl                                                                            Epoxy ( .sub.-- E)-2-Butenyl                                           650                                                                               n-Propyl                                                                            Epoxy ( .sub.-- E)-3-Chloro-2-propenyl                                                           1.35(t), 2.0(m), 3.3(s)                              651                                                                               n-Propyl                                                                            Epoxy Propargyl                                                        652                                                                               n-Butyl                                                                             Cl    Ethyl                                                            653                                                                               n-Butyl                                                                             Cl    Allyl                                                            654                                                                               n-Butyl                                                                             Cl    ( .sub.-- E)-2-Butenyl                                           655                                                                               n-Butyl                                                                             Cl    ( .sub.-- E)-3-Chloro-2-propenyl                                 656                                                                               n-Butyl                                                                             Cl    Propargyl                                                        657                                                                               n-Butyl                                                                             Br    Ethyl                                                            658                                                                               n-Butyl                                                                             Br    Allyl                                                            659                                                                               n-Butyl                                                                             Br    ( .sub.-- E)-2-Butenyl                                           660                                                                               n-Butyl                                                                             Br    ( .sub.-- E)-3-Chloro-2-propenyl                                 661                                                                               n-Butyl                                                                             Br    Propargyl                                                        662                                                                               n-Butyl                                                                             OH    Ethyl                                                            663                                                                               n-Butyl                                                                             OH    Allyl                                                            664                                                                               n-Butyl                                                                             OH    ( .sub.-- E)-2-Butenyl                                           665                                                                               n-Butyl                                                                             OH    ( .sub.-- E)-3-Chloro-2-propenyl                                 666                                                                               n-Butyl                                                                             OH    Propargyl                                                        667                                                                               n-Butyl                                                                             Epoxy Ethyl                                                            668                                                                               n-Butyl                                                                             Epoxy Allyl                                                            669                                                                               n-Butyl                                                                             Epoxy ( .sub.-- E)-2-Butenyl                                           670                                                                               n-Butyl                                                                             Epoxy ( .sub.-- E)-3-Chloro-2-propenyl                                 671                                                                               n-Butyl                                                                             Epoxy Propargyl                                                        __________________________________________________________________________

                                      TABLE 7                                      __________________________________________________________________________     No.                                                                               A   B X R.sup.1                                                                             R.sup.2                                                                            R.sup.3 R.sup.4                                                                    R.sup.5                                                                            R.sup.6                                                                             R.sup.7                                                                          R.sup.8                                     __________________________________________________________________________     673                                                                               NOR.sup.8                                                                          O H C.sub.3 H.sub.7 CO                                                                  Propyl                                                                             --O--                                                                              --CH.sub.2 OC.sub.2 H.sub.4 --                                                          H Ethyl                                                                               0.90(t), 1.0(t), 1.24(t)               674                                                                               NOR.sup.8                                                                          O H Benzoyl                                                                             Propyl                                                                             O   CH.sub.2 OC.sub.2 H.sub.4                                                               H Ethyl                                                                               0.86(t), 1.09(t), 7.3-8.2(m)           675                                                                               NOR.sup.8                                                                          O H Acetyl                                                                              Propyl                                                                             O   CH.sub.2 OC.sub.2 H.sub.4                                                               H Ethyl                                                                               0.88(t), 1.25(t),                      __________________________________________________________________________                                             2.19(s)                           

The cyclohexenone derivatives of the formula I, and their salts, may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.

For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, and paraffin, tetrahydrocarbons such as methanol, ethanol, propanol, butanol, chloroform, carbon tetrachloride, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of ligninsulfonic acid, naphthalenesulfonic acids, phenolsulfonic acids, alkylaryl sulfonates, alkyl sulfates, and alkyl sulfonates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, alkali metal and alkaline earth metal salts of fatty acids, salts of sulfated hexadecanols, heptadecanols and octadecanols, salts of sulfated fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol or formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin, sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate and ureas, and vegetable products such as grain flours, bark meal, wood meal and nutshell meal, cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably from 0.5 to 90, % by weight of active ingredient.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 647 is mixed with 10 parts by weight of N-methyl-α-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 648 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of active ingredient.

III. 20 parts by weight of compound no. 650 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of active ingredient.

IV. 20 parts by weight of compound no. 637 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210 and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of active ingredient.

V. 20 parts by weight of compound no. 638 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-α-sulfonic acid, 17 parts by weight of the sodium salt of a ligninsulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight of active ingredient.

VI. 3 parts by weight of compound no. 640 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of active ingredient.

VII. 30 parts by weight of compound no. 478 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

VIII. 20 parts of compound no. 480 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

IX. 10 parts by weight of compound no. 440 is mixed with 90 parts by weight of a mixture consisting of 93 parts by weight of xylene and 7 parts by weight of the adduct of 8 moles of ethylene oxide and 1 mole of nonylphenol. A solution is obtained containing 10 wt % of the active ingredient.

The active ingredients, or agents containing them, may be applied pre- or postmergence. If certain crop plants tolerate the active ingredients less well, application techniques may be used in which the herbicidal agents are sprayed from suitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).

The amounts of active ingredient applied depends on the time of the year, the plants to be combated and their growth stage, and varies from 0.01 to 3 kg/ha, but is preferably from 0.05 to 0.5 kg/ha.

The action of the cyclohexenone derivatives of the formula I on plant growth is demonstrated in greenhouse experiments.

The vessels employed were plastic flowerpots having a volume of 300 cm³, and which were filled with a sandy loam containing about 3.0% humus. The seeds of the test plants were sown shallow, and separately, according to species. For the preemergence treatment, the active ingredients were applied to the surface of the soil immediately after the seeds had been sown. The compounds were emulsified or suspended in water as vehicle, and sprayed through finely distributing nozzles. The application rate was 3.0 kg of active ingredient per hectare. After the agents had been applied, the vessels were lightly sprinkler-irrigated to induce germination and growth. Transparent plastic covers were then placed on the vessels until the plants had taken root. The cover ensured uniform germination of the plants, insofar as this was not impaired by the active ingredients.

For the postemergence treatment, the plants were first grown in the vessels to a height of from 3 to 15 cm, depending on growth form, before being treated. For this treatment, either plants which had been sown directly in the pots and grown there were selected, or plants which had been grown from seedlings and were transplanted to the pots a few days before treatment. The application rate for postemergence treatment was 0.125 kg of active ingredient per hectare. No covers were placed on the vessels in this method.

The pots were set up in the greenhouse - species from warmer areas at from 20° C. to 35° C., and species from moderate climates at 10° to 25° C. The experiments were run for 2 to 4 weeks. During this period, the plants were tended and their reactions to the various treatments assessed. The scale used for assessment was 0 to 100, 0 denoting no damage or normal emergence, and 100 denoting nonemergence or complete destruction of at least the visible plant parts.

The plants used in the experiments were Alopecurus myosuroides, Avena fatua, Avena sativa, Digitaria sanguinalis, Echinochloa crus-galli, Lolium multiflorum, Medicago sativa, Setaria italica, Sinapis alba, Sorghum halepense, Triticum aestivum, and Zea mays.

Grasses from the Gramineae family were well combated with a preemergence application of 3.0 kg/ha of, for example, compounds 647, 648, 650, 637, 638, 640, 478 and 440. Sinapis alba (broadleaved crop plant) suffered no damage whatsoever.

Compounds 647, 648, 650 and 401 are suitable, at a rate of 0.125 kg/ha, for controlling, postemergence, a broad spectrum of unwanted grassy plants. Volunteer crop plants from the Gramineae family are also combated. Alfalfa--a broadleaved crop plant--remain completely uninfluenced.

Unwanted grassy species are well combated by postemergence applications of active ingredients 438, 439 and 674; wheat remains unaffected.

In view of the spectrum of weeds which can be combated, the tolerance of the active ingredients according to the invention by crop plants, the desired influence on the growth of crop plants, and in view of the numerous application methods possible, the compounds according to the invention may be used in a large number of crop plants.

The following crops may be mentioned by way of example:

    ______________________________________                                         Botanical name          Common name                                            ______________________________________                                         Allium cepa             onions                                                 Ananas comosus          pineapples                                             Arachis hypogaea        peanuts                                                                        (groundnuts)                                           Asparagus officinalis   asparagus                                              Beta vulgaris spp. altissima                                                                           sugarbeets                                             Beta vulgaris spp. rapa fodder beets                                           Beta vulgaris spp. essculenta                                                                          table beets,                                                                   red beets                                              Brassica napus var. napus                                                                              rapeseed                                               Brassica napus var. napobrassica                                                                       swedes                                                 Brassica napus var. rapa                                                                               turnips                                                Brassica rapa var. silvestris                                                                          tea plants                                             Camellia sinensis                                                              Carthamus tinctorius    safflower                                              Carya illinoinensis     pecan trees                                            Citrus limon            lemons                                                 Citrus maxima           grapefruits                                            Citrus reticulata       mandarins                                              Citrus sinensis         orange trees                                           Coffea arabica (Coffea canephora,                                                                      coffee plants                                          Coffea liberical)                                                              Cucumis melo            melons                                                 Cucumis sativus         cucumbers                                              Cynodon dactylon        bermudagrass                                           Daucus carota           carrots                                                Elaeis guineensis       oil palms                                              Fragaria vesca          strawberries                                           Glycine max             soybeans                                               Gossypium hirsutum (Gossypium arboreum,                                                                cotton                                                 Gossypium herbaceum, Gossypium vitifolium)                                     Helianthus annuus       sunflowers                                             Helianthus tuberosus    Jerusalem                                                                      artichoke                                              Hevea brasiliensis      rubber plants                                          Hordeum vulgare         barley                                                 Humulus lupulus         hops                                                   Ipomoea batatas         sweet potatoes                                         Juglans regia           walnut trees                                           Lactua sativa           lettuce                                                Lens culinaris          lentils                                                Linum usitatissimum     flax                                                   Lycopersicon lycopersicum                                                                              tomatoes                                               Malus spp.              apple trees                                            Manihot esculenta       cassava                                                Medicago sativa         alfalfa (lucerne)                                      Mentha piperita         peppermint                                             Musa spp.               banana plants                                          Nicotiana tabacum (N. rustica)                                                                         tobacco                                                Olea europaea           olive trees                                            Oryza sativa            rice                                                   Phaseolus lunatus       limabeans                                              Phaseolus mungo         mungbeans                                              Phaseolus vulgaris      snapbeans,                                                                     green beans,                                                                   dry beans                                              Pennisetum glaucum      pearl millet                                           Petroselinum crispum spp. tuberosum                                                                    parsley                                                Picea abies             Norway spruce                                          Abies alba              fir trees                                              Pinus spp.              pine trees                                             Pisum sativum           English peas                                           Prunus avium            cherry trees                                           Prunus domestica        plum trees                                             Prunus dulcis           almond trees                                           Prunus persica          peach trees                                            Pyrus communis          pear trees                                             Ribes sylvestre         redcurrants                                            Ribes uva-crispa        gooseberries                                           Ricinus communis        castor-oil plants                                      Saccharum officinarum   sugar cane                                             Secale cereale          rye                                                    Sesamum indicum         sesame                                                 Solanum tuberosum       Irish potatoes                                         Spinacia oleracea       spinach                                                Theobroma cacao         cacao plants                                           Trifolium pratense      red clover                                             Triticum aestivum       wheat                                                  Vaccinium corymbosum    blueberries                                            Vaccinium vitis-idaea   cranberries                                            Vicia faba              tick beans                                             Vigna sinensis (V. unguiculata)                                                                        cow peas                                               Vitis vinifera          grapes                                                 Zea mays                Indian corn,                                                                   sweet corn, maize                                      ______________________________________                                    

To increase the spectrum of action and to achieve synergistic effects, the cyclohexenone derivatives of the formula I may be mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples or suitable mixture components are diazines, 4H-3, 1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, quinolinecarboxylic acid derivatives, etc.

It may also be useful to apply the compounds of the formula I, or herbicidal agents containing them, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi or bacteria. The compounds may also be mixed with solutions of mineral salts used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added. 

We claim:
 1. A cyclohexenone derivative of the formula ##STR12## where A is oxygen or NOR⁸, where R⁸ is alkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, alkynyl of 3 or 4 carbon atoms, haloalkyl or haloalkenyl of 2 to 4 carbon atoms and 1 to 3 halogen atoms, chlorothienyl or alkoxyalkyl of 2 to 4 carbon atoms,B is S, SO or SO₂, X is hydrogen or methoxycarbonyl, R¹ is hydrogen, alkanoyl of 2 to 18 carbon atoms or benzoyl or an inorganic or organic cation, R² is alkyl of up to 4 carbon atoms, R³ and R⁴, independently of each other, are each hydroxyl, chlorine, bromine, carboxylalkylthio, alkylcarbonylthio, alkylcarbonyloxy each of up to 4 carbon atoms or one of R³ and R⁴ is alkoxy of up to 3 carbon atoms and the other is hydroxyl or one of R³ and R⁴ is alkylthio of up to 3 carbon atoms and the other is hydroxyl, or together R³ and R⁴ form an epoxy group, R⁵ and R⁶, independently of each other, are each hydrogen or methyl or R⁵ and R⁶ are together a methyleneoxyethylene group, and R⁷ is hydrogen or methyl.
 2. A cyclohexenone derivative as set forth in claim 1, where A is NOR⁸, X is hydrogen, R¹ is hydrogen, R² is ethyl or propyl, each of R³ and R⁴ is bromine or R³ and R⁴ together are an epoxy group, each of R⁵ and R⁶ is hydrogen or R⁵ and R⁶ together are a methyleneoxyethylene group, R⁷ is hydrogen, and R⁸ is ethyl, allyl, chloropropenyl or butenyl.
 3. A herbicide containing an inert additive and an effective amount of a compound of the formula ##STR13## where A is oxygen or NOR⁸, where R⁸ is alkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, alkynyl of 3 or 4 carbon atoms, haloalkyl or haloalkenyl of 2 to 4 carbon atoms and 1 to 3 halogen atoms, chlorothienyl or alkoxy of 2 to 4 carbon atoms,B is S, SO or SO₂, X is hydrogen or methoxycarbonyl, R¹ is hydrogen, alkanoyl of 2 to 18 carbon atoms or benzoyl or an inorganic or organic cation, R² is alkyl of up to 4 carbon atoms, R³ and R⁴, independently of each other, are each hydroxyl, chlorine, bromine, carboxylalkylthio, alkylcarbonylthio, alkylcarbonyloxy each of up to 4 carbon atoms or one of R³ and R⁴ is alkoxy of up to 3 carbon atoms and the other is hydroxyl or one of R³ and R⁴ is alkylthio of up to 3 carbon atoms and the other is hydroxyl, or together R³ and R⁴ form an epoxy group, R⁵ and R⁶, independently of each other, are each hydrogen or methyl or R⁵ and R⁶ are together a methyleneoxyethylene group, and R⁷ is hydrogen or methyl.
 4. A herbicide as set forth in claim 3 containing an effective amount of a compound of the formula I, where A is NOR⁸, X is hydrogen, R¹ is hydrogen, R² is ethyl or propyl, each of R³ and R⁴ is bromine or R³ and R⁴ together are an epoxy group, R⁵ and R⁶ are each hydrogen or R⁵ and R⁶ together are a methyleneoxyethylene group, R⁷ is hydrogen, and R⁸ is ethyl, allyl, chloropropenyl or butenyl.
 5. A process for combating the growth of unwanted plants, wherein the unwanted plants or the area to be kept free from unwanted plant growth are treated with a herbicidally effective amount of a compound of the formula ##STR14## where A is oxygen or NOR⁸, where R⁸ is alkyl of 1 to 4 carbon atoms, alkenyl of 3 or 4 carbon atoms, alkynyl of 3 or 4 carbon atoms, haloalkyl or haloalkenyl of 2 to 4 carbon atoms and 1 to 3 halogen atoms, chlorothienyl or alkoxyalkyl of 2 to 4 carbon atoms,B is S, SO or SO₂, X is hydrogen or methoxycarbonyl, R¹ is hydrogen, alkanoyl of 2 to 18 carbon atoms or benzoyl or an inorganic or organic cation, R² is alkyl of up to 4 carbon atoms, R³ and R⁴, independently of each other, are each hydroxyl, chlorine, bromine, carboxylalkylthio, alkylcarbonylthio, alkylcarbonyloxy each of up to 4 carbon atoms or one of R³ and R⁴ is alkoxy of up to 3 carbon atoms and the other is hydroxyl or one of R³ and R⁴ is alkylthio of up to 3 carbon atoms and the other is hydroxyl, or together R³ and R⁴ form an epoxy group, R⁵ and R⁶, independently of each other, are each hydrogen or methyl or R⁵ and R⁶ are together a methyleneoxyethylene group, and R⁷ is hydrogen or methyl. 